Colouration of polymeric materials

ABSTRACT

Grey dyed polyester photographic film support dyed with at least two dye components selected from 6-paratoluidino-3-methyl 1&#39;&#39;9&#39;&#39; anthrapiridone, indanthrone, tetrachloro phthalo perinone and 1,4-bis(4-n-butyl-anilino)-5,8-dihydroxy anthraquinone.

United States Patent Whyte *Nov. 5, 1974 COLOURATION 0F POLYMERIC [51] Int. Cl C08g 51/04 MATERIALS [58] Field of Search 260/40 P, 40 R [75] Inventor: James Lyon Whyte, Welwyn Garden City, England {56] References Cited [73] Assignee: Imperial Chemical Industries UNITED STATES PATENTS Limited, London 3,489,7'3 H1970 Bowman Cl 11 260/40 P 3,728,124 4/1973 Whyte 96/84 R 1 Notice: The portion of the term of this patent subequm to 1990* Primary Examiner-Morris Licbman has been dlsclamed' Assistant Examiner-S. M. Person 22 i 1 1973 Attorney, Agent, or FirmCuShman, Darby &

Cushman [21] Appl. No.: 351,611

Related US. Application Data [57] ABSTRACT [62] Division of Ser. No. 94,564, Dec. 2, 1970, Pat. No. G y d ed polyester photographic film support dyed 3,728,124- with at least two dye components selected from 6- 0 paratoluidino-3-methyl 1'9 anthrapiridone, indan- [30] Fore'gn Apphcanon Pnonty Data throne, tetrachloro phthalo perinone and l,4-bis(4-n- Dec. 5, 1969 Great Britain 59512/69 US. Cl 260/40 R, 260/40 P butyl-anilino)-5,8-dihydr0xy anthraquinone.

3 Claims, No Drawings COLOURATION OF POLYMERIC MATERIALS This is a division, of application Ser. No. 94,564 filed Dec. 2, 1970, now US. Pat. No. 3,728,124.

The present invention relates to the colouration of polymeric materials, and in particular to such coloured polymeric materials suitable for the production of films. The invention is more particularly concerned with coloured film suitable for use as a photographic film base.

Film supports for cine or recording films should generally be resistant to halation and light piping effects. This can be achieved by tinting the film with a grey dye. The dyes chosen for this purpose should be heat stable at the temperatures to which the polymeric material is subjected after the dye has been incorporated.

According to the present invention there is provided a coloured organic polymeric material containing a grey dye, said dye comprising at least two components selected from 6-paratoluidino-3-methyl l 9 anthrapyridone, indanthrone, tetrachloro phthalo perinone and l,4-bis(4-n-butyl-anilino)-5,8-dihydroxy anthraquinone.

We find that useful grey dyes for forming photographic film supports are obtained when one of the dye components is indanthrone.

In another aspect of the invention a useful photographic film support is coloured with a dye comprising Generally the grey dye may contain two or three of the dye components mentioned hereinabove. Each of the dye components employed in colouring the polymeric material may be present in an amount in the range 0.005 to 0.15 percent by weight of the polymeric material. When light piping and halation effects must be reduced, e.g., in cine film, higher amounts of the dye components may be employed, e.g., up to 0.15 percent. When light piping only must be reduced, e.g., in recording film, lower concentrations of the dye components may be employed, e.g., up to 0.05 percent.

Generally the components of the dye may be used collectively in an amount in the range 0.03 to 0.15 percent by weight of the polymeric material, although some dyes may be employed in slightly higher collective proportions.

The polymeric materials and photographic film supports which may be coloured according to the invention include materials such as cellulose esters and cellulose mixed esters or thermoplastics materials such as polyamides, polycarbonates, polymers and copolymers of propylene, and polyesters such as polyethylene terephthalate. We particularly prefer to make photographic film supports from polyethylene terephthalate and find that the dyes employed according to the invention are suitable for colouring such supports since they are stable at the temperatures normally employed in manufacturing the polymeric material and in producing films therefrom.

The dye may be incorporated into the polymeric material, particularly polyesters such as polyethylene terephthalate, by blending in a known manner with the powdered or granulated polyester. Alternatively the dye may be incorporated into the polymeric material during its manufacture. This procedure may be adopted for colouring polyesters such as polyethylene terephthalate by adding the dye components to the polycondensation reaction since the dyes are stable at the temperatures employed for such reactions.

When a polyester filmsupport is employed for photographic uses it should be biaxially oriented and heat set. This may, for example, be accomplished in an apparatus constructed to stretch continuous lengths of film-in the machine and transverse directions. In such apparatus a flat film is extruded on to a rotating drum on which it is quenched and is then oriented in the machine direction by being drawn between two sets of nip or capstan rollers, the second set rotating at a speed greater than the speed of rotation of the first set by an amount equal to the required draw ratio. The slow rollers may be heated to the desired drawing temperature or alternatively the film may be heated between the fast and slow rollers by radiant heat. The film may then be drawn in the transverse direction in a stenter apparatus conveniently located in a heated oven. The biaxially oriented film may then be heat set and if desired dimensionally stabilised in a known manner.

The film supports produced according to the present invention may be coated with photographic emulsion layers such as light sensitive silver halide coatings. Since polyester film supports are highly hydrophobic and the silver halide emulsion layers are highly hydrophilic the film support is normally treated in order to enhance the adhesion to the emulsion layer. The treatment which is commonly employed involves applying an anchoring layer, usually termed a subbing layer, to the film support and then applying the emulsion layer over the subbing layer. The subbing layer may, for example, be applied as an aqueous composition of a vinylidene chloride polymer or copolymer, for example, the terpolymer of vinylidene chloride, methyl acrylate and itaconic acid.

In order that the invention may be more readily understood it is further illustrated in the following nonlimiting Examples, in which parts are measured by weight.

EXAMPLE 1 parts of bis(B-hydroxy ethyl) terephthalate, prepared in a known manner, were melted under oxygenfree nitrogen in a heated stainless steel vessel having a vacuum take off condenser and stirrer. 0.04 parts of antimony trioxide catalyst and a grey dye comprising by weight 0.021 1 part indanthrone and 0.0255 part tetrachlorophthalo perinone were added. The mass was agitated and the temperature raised as rapidly as possible. Ethylene glycol distilled along the vacuum take off and was condensed and collected. When the temperature had reached 245C the vacuum pump was started to reduce the pressure at a rate which gave a reduced pressure of 1 mm as the temperature reached 270275C. The reaction was continued at 278C and a pressure of less than 1 mm for 2.3 hours. The molten polymer was extruded through a bottom outlet in the vessel by nitrogen pressure applied above its surface.

Film was produced from the polymer in a conventional manner by extrusion on to a quenching roll followed by longitudinal orientation by stretching between a set of slow rollers and a set of fast rollers, transverse orientation by stretching in a stenter oven and finally heat setting in a stenter oven. The film was stretched to 3.5 times its original length in the longitudinal and transverse directions.

A subbing layer comprising an aqueous latex of 92 percent vinylidene chloride, 6 percent methyl acrylate and 2 percent itaconic acid was applied to the film after it had been heat set. A gelatin subbing layer followed by a sensitive silver halide emulsion layer were then ap plied to the film in a conventional manner.

The film was subjected to the normal processing solutions employed in processing photographic materials.

The grey colour of the film was observed throughout the various stages described in this Example and was not affected by the conditions employed in the production of the polymer, its formation into a film and its treatment with photographic processing solutions.

EXAMPLE 2 Example 1 was repeated with the substitution of a grey dye comprising:

0.012 part 6-paratoluidino-3-methyl l '9' anthrapyridone 0.020 part indanthrone. The grey film produced with this dye had a colour which was unaffected by the conditions employed in the production of the polymer, its formation into a film V and its treatment with photographic processing solutions.

4 anthrapyridone 0.010 part 6-paratoluidino-3-methyl 1'9 anthrapiridone The grey film produced with this dye had a colour which was unaffected by the conditions employed in the production of the polymer, its formation into a film and its treatment with photographic processing solutions.

I claim:

1. A method of producing a polyester film which is resistant to light piping by including therein a grey dye mixture which consists of up to 0.15 percent by weight of the polyester of at least one dye selected from 6- paratoluidino-3-methyl 1'9 anthrapyridone and tetrachlorophthalo perinone and up to 0.15 percent by weight of the polyester of at least one dye selected from indanthrone and 1,4 bis (4-n-butyl anilino)-5,8, dihydroxy anthraquinone, said method comprising including the dye mixture in the polyester-forming reaction mixture, subjecting said reaction mixture to polycondensation while agitating to form said polyester with the dye mixture uniformly incorporated therein and then extruding the polyester to form said film.

2. The film obtained by the method of claim 1.

3. The method of claim 1 wherein the dye mixture consists of 6-paratoluidino-3-methyl 1'9 anthrapyridone and l,4-bis(4-n-butyl-anilino)-5'8-dihydroxy anthraquinone. 

1. A METHOD OF PRODUCING A POLYESTER FILM WHICH IS RESISTANT TO LIGHT PIPING BY INCLUDING THEREIN A GREY DYE MIXTURE WHICH CONSISTS OF UP TO 0.15 PERCENT BY WEIGHT OF THE POLYESTER OF AT LEAST ONE DYE SELECTED FROM 6-PARATOLUIDINO-3-METHYL 1''9'' ANTHRAPYRIDONE AND TERACHLOROPHTHALO PERINONE AND UP TO 0.15 PERCENT BY WEIGHT OF THE POLYESTER OF AT LEAST ONE DYE SELECTED FROM INDANTHRONE AND 1,4 BIS (4-N-BUTYL AMILINO)-5,8, DIHYDROXY ANTHARQUINONE, SAID METHOD COMPRISING INCLLUDING THE DYE MIXTURE IN THE POLYESTER-FORMING REACTION MIXTURE, SUBJECTING SAID REACTION MIXTURE TO POLYCONDENSATION WHILE AGITATING TO FORM SAID POLYESTER WITH THE DYE MIXTURE UNIFORMLY INCORPORATED THEREIN AND THEN EXTRUDING THE POLYESTER TO FORM SAID FILM.
 2. The film obtained by the method of claim
 1. 3. The method of claim 1 wherein the dye mixture consists of 6-paratoluidino-3-methyl 1''9'' anthrapyridone and 1,4-bis(4-n-butyl-anilino)-5''8-dihydroxy anthraquinone. 